Reaction on carbonaceous materials with hydrogenating gases



Patented 1 05.20, 1940 PATENT OFFICE REACTION N oARBoNAcEoUs MATERIALSWITH nrnnoonnn'rmc. GASES Mathias Pier, Heidelberg, and Walter Simon andWalter Kroenig, Ludwigshafen-on-the-Rhine, Germany, assignors toStandard-I. G. Company, Linden, N. J a corporation of Delaware NoDrawing. Original application March 1,

1933, Serial No. 659,168. Divided and this ap- 'plication October 6,1937, Serial No. 167,555.

In Germany March 9, 1932 5 Claims.

The subject-matter of the present application has been divided out fromour copending application Ser. No. 659,168, filed March 1, 1933, whichrelates to the production of valuable hydrocarbons, for example those oflow boiling point range from distillable carbonaceous materials, such ascoal of all varieties, including pit coal and brown coal, shale,bituminous sands, tar,- mineral oils, shale oils, their distillation,conversion and extraction products and residues and the like, byhydrogenation reactions carried out with added hydrogenating gases, suchas hydrogen or gases containing or supplying hydrogen and underpressure, preferably in circular course, in contact with catalysts, andin which is claimed the step of adding to the initial materials solidsimple acid-salts of polyvalent metals and sulfuric, phosphoric andboric acids.

We have found that the conversion of distillable carbonaceous materialscontaining compounds having a basic and more particularly an alkalinereaction into valuable hydrocarbons by the abovementioned treatment canbe effected in a'very advantageous manner by adding to the initialcarbonaceous materials before or during the said conversion acids oracid salts in such an amount that at least 80 per cent of the said basiccompounds are neutralized.

As examples of acids to be employed according to the present inventionmay be mentioned inorganic oxygen containing acids of sulphur ornitrogen and the anhydrides of said inorganic acids, if desired,together with water, further hydrohalic acids, 'e. g. hydrochloric orhydriodic acid, phosphoric acid and organic sulphonic and carboxylicacids.

It is of particular advantage to add simple solid acid salts to theinitial materials. As examples of these acid salts may be mentionedthose of polyvalent metals, such as tin, molybdenum, tungsten,manganese, magnesium, rhenium, zinc, cadmium, aluminum, vanadium orchromium.

Good results are for example obtained with acid magnesium phosphate,acid zinc phosphate, acid zinc borate, acid cadmium phosphate, acidvanadyl phosphate or acid chromic phosphate. The acid salts of sulphuricacid and the salts of pyro sulphuric acid also come into consideration.The acid alkali metal salts may also be employed, in particular acidlithium phosphate, but as a general rule the results obtained'therewithare not so good as those obtained with the salts herelnbefore referredto, and these latter should therefore usually be employed by preference.As examples of the said inorganic acids of sulphur or nitrogen may bementioned sulphuric acid, sulphurous acid and nitric acid, or theorganic carboxylic acids, acetic acid, formic acid and oxalic acid, andof the organic sulphonic acids benzene sulphonic acid, naphthalenesulphonic acid or sulphonated unsaturated hydrocarbons. In additionmetals or compounds other than the "acid salts hereinbeforereferred toof metals of the 2nd to the 8th groupof the periodic system, inparticular of the 6th group, such as for example sulphides, halides,phosphides, oxides,

carbonates or oxalates of zinc, aluminum, titanium, tin, lead, vanadium,bismuth, chromium, molybdenum, tungsten, uranium, manganese, rhenium,iron, nickel or cobalt may be employed. Said additional metals orcompounds thereof are usually added in amounts between about 0.05 and 10per cent by weight of the carbonaceous material undergoing treatment,for example between 0.1 and 5 per cent.

When adding the said acid substances in the destructive hydrogenation ofoils as for example tar or mineral oils, or fractions thereof, thesplitting action as well as the hydrogenation efiect is increased. Alsothe amounts of asphalts present in the reaction products are lowercompared with processes working without'these acid additions.

The compounds having a basic reaction contained in the initial materialhave a restraining action on the pressure hydrogenation and tend todiminish the action of the catalysts of the type usually employed, inparticularthose which have a non-basic character. By neutralizing thesaid compounds wholly or nearly so they are rendered harmless and evenan excess of the said acids or acid salts above that required forneutralization may be employed. At the same time an improvement in thequality of the liquefied product (for example a reduction of the asphaltcontent) and an increase in the yield thereof results. -The amount ofacid or acid salt which has to be added to completely neutralize thecompounds having a basic reaction contained in the initial material, canbe determined by simple preliminary trials. For example, a sample of theinitial material to be destructively hydrogenated may be treated with anexcess of an appropriately diluted acid at elevated temperatures and thepart of the acid which is not used up for the neutralization determinedafter filtration by titration of the filtrate with alkali.

It has been found advantageous in many cases to employ exactly thatamount of acid substances (which includes substances which are not bythemselves acid, but which give rise to an acid reaction -when dissolvedin water) required to neutralize the constituents of the initialmaterials having a. basic reaction, or an amount of acid substancesexceeding or falling short of said amount by not more than 20 per centbased. on the total amount of acid substance employed.

The acids or acid salts may be added to the initial materials before orafter the preheating. The acids may for example be atomized intothe,reaction chamber together with or at the same time as the preheatedcarbonaceous materials are introduced thereinto. The acid substancesemployed according to the present invention may also be admixed with theinitial materials in suitable intermediate vessels, which may bearranged before the reaction chamber or in the preheating system.

The acids or acid salts may also be added by soaking porous materialssuchas active carbon, active silica, pumice stone, etc., with said acidsor solutions of said acids or acid salts and supplying these to thereaction chamber.,

The expression tended to comprise the most various reactions and thecatalysts employed in accordance with ment by destructive hydrogenationwith hydrogenating gases of carbonaceous materials, such as coal-of allvarieties, including lignite, other solid carbonaceous materials such aspeat, shales and wood, mineral oils, tars and the distillation,

conversion and extraction products thereof The said treatment may beused to produce hydrocarbons of all sorts, such as motor fuels, middleoils, kerosene and lubricating oils. The said expression also includesthe removal of non-hydrocarbon impurities, such as sulphuroroxygen-containing substances or nitrogen compounds by the action ofhydrogen or gases containing or supply--v ing hydrogen from crudecarbonaceous materials, for example the refining by treatment withhydrogen of crude benzol, of crude motor fuels or of lubricating oils.The said expression further includes the conversion of oxygenorsulphurcontaining organic compounds to produce the correspondinghydrocarbons or hydrogenated hydrocarbons, for example the conversion ofphenols or cresols into the corresponding cyclic hydrocarbons orhydrogenation products thereof. Finally it includes the hydrogenaton ofunsaturated compounds and more particularly of unsaturated hydrocarbonsor of aromatic compounds and more particularly of aromatic hy-"drocarbons,vfor example to produce hydroaromatic hydrocarbons.

The said reaction with hydrogen or hydrogen containing gases are usuallycarried out at temperatures between 250 and 700 C. and as a rule betweenabout 380 and 550 C. The pressures employed are usually in excess of 20atmospheres and as a rule preferably in excess of 50 atmospheres. Insome reactions, however, for example in the refining of crude benzol,relative-' 1y low pressures, for example, of the order of 40 atmospheresmay be employed. Generally, however, pressures of about 100, 200, 300,500 and in some cases even 1000 atmospheres come into consideration. I vr 'Ihev amount of hydrogen maintained in the reaction space and partsconnected therewith, if any, varies greatly with the nature of the'parhydrogenation reactio when employed in the present application isinthe result in view. In general, 400, 600, 1000 cubic meters or more ofhydrogen, measured under normal conditions of temperature and pressure,per ton of carbonaceous materials treated may be used.

It is particularly advantageous to operate by continuously introducingfreshcarbonaceous material into the reaction vessel and to continuouslyremoveeproducts therefrom. If desired several reaction vessels may beemployed in which different conditions of temperature and/or pressuremay, if necessary, be maintained and in which different reactionproducts may be re-.

moved behind any of the reaction vessels. Materials which have not beensufliciently reacted on may be recycled or treated in 'a furtherreaction vessel.

The carbonaceous materials may be treated in the reaction in the liquid,solid or gaseous phase as required.

The reaction is advantageously carried out with streaming hydrogenatinggases.

The gases for use in the reaction may consist of hydrogen alone or ofmixtures'containing hydrogen, for example, a mixture of hydrogen withnitrogen, or water gas, or of hydrogen mixed with carbon dioxide,sulphuretted hydrogen, water vapor 'or methane or other. hydrocarbons.

The following examples will further illustrate the nature of theinvention but it should be understood that the invention is not limitedto the said examples. The percentages are by weight unless otherwisestated. e

Example 1 The vapors of a middle oil, obtained'by de- I structivehydrogenation under pressure of petroleum, are passed together withhydrogen under 200 atmospheres pressure and at a temperature of 430 9.over a catalyst rigidly arranged in a high-pressure-chamber andconsisting of 50 parts of tungsten. sulphide and 50 parts of molybdenumbromide. The obtained product consists to the extent of,40 per cent ofconstituents boiling up to 180 C. When adding to the middle'oil beforethe treatment formic acid in an amount of 2 per cent calculated on themiddle oil, a product is obtained consisting to the extent of 55 percent of constituents boiling up to 180 C. The remainder is employable asilluminating oil or Diesel oil.

Example 2 1 A paste consisting of 2 parts -of a finely ground driedbrown coal and 1 part of a heavy oil (boiling above 325 0.) obtainedfrom the same coal by pressure hydrogenation is arranged in thin layerson plates superposed in a high'pressure autoclave. As a catalyst 2 percent 'of tungsten sulphide is added to the coal. The autoclave, throughwhich hydrogen continually flows under 250 atmospheres pressure, isheated in one hour amount as is necessary for the neutralization of thesaid alkaline constituents and the coal is treated as indicated, 96 percent of the carbon of the coal is converted to valuable, mainly liquidhydrocarbons with only 6 per cent of asphalt.

For-neutralizing the coal it may be suspended in water and then treatedwith sulphur dioxide introduced into the suspension. If comminuted notdried coal is employed the sulphur dioxide is simply passed thereover.The coal thus treated is then dried and pasted up with'the aforesaidheavy oil. Also the paste of coal and heavy oil may be first preparedand then only be treated with sulphur dioxide.

Example 3 A petroleum freed from constituents boiling below 325 C. issubjected to a pressure hydrogenation at 445 C. and under a hydrogenpressure of 250 atmospheres in the presence of 20 per cent of a catalystground to a colloidal state of subdivision suspended in oil, andconsisting of molecular amounts of molybdic acid, acid zinc phosphateand acid magnesiumphosphate.v The speed of flow is so selected that pereach volume of reaction space one volume of initial material passesthrough per hour. In a separator annexed to the high-pressure-chamber,the temperature of which amounts to 435 C., a definite level of liquidis maintained. The unvaporized product collected therein is led backtogether with the catalyst suspended therein while still hot to thereaction chamber. On cooling the gases and vapors which leave theseparator, a product is obtained, which consists to the extent of 50 percent of constituents boiling up to 325 C.; the constituents obtainedtherefrom by distillation which boil above 325 C. are led back to thehighpressure-chamber. When adding a mixture. consisting of molecularamounts of molybdic acid, zinc oxide and magnesium oxide, the sameresults can only be obtained by lowering the throughput to 80 per centof that used with the acid catalyst.

Emample 4 Brown-coal is finely ground and made into a paste with anequal amount of heavy oil obtained from the same coal by destructivehydrogenation and is mixed with 0.1 per cent (based on the coal) ofchromic acid. *This coal paste is then heated together with hydrogenunder pressure to 455 C. and passed through a reaction vessel. 93 percent of the carbon of the coal is obtained thereby in the form ofvaluable mainly liquid hydrocarbons, of which the products boiling above325 C. contain 7 per cent asphalts. When adding on the other hand a likeamount of acid chromium phosphate as catalyst and working underotherwise similar reaction conditions, then 96 per cent of the carbon ofthe coal is liquefied and the liquid products boiling above 325 C. onlycontain 5 per cent of asphalts.

Example 5 Finely ground pit-coal is made into a paste with an equalamount of heavy oil boiling above 325 0., obtained by destructivehydrogenation of the same coal. Vanadium oxide is added to the paste inan amount of 0.05 per cent calculated on the coal. The mixture is thenheated together with hydrogen under a pressure of 200 atmospheres to 455C. and passed through a reaction vessel. 89 per cent of the carbon ofthe coal is obtained thereby in the form of liquid products of which theproducts boiling above 325 C. contain percent asphalts. When adding inthe place of the abovementioned catalyst acid vanadium phosphate andworking under otherwise similar conditions, 92 per cent of .the carbonof the coal is obtained in the form of liquid products of phate.

Example 6 A fraction of petroleum boiling above 325 C. is heatedtogether with hydrogen under a pressure of 200 atmospheres to 460 C. andthe mixture is in a reaction vessel brought into contact with 20 percent (calculated on the amount of petroleum) of finely divided acidchromium phos- The reaction participants are then passed into aseparator, from which a product passes oil? in the vaporous form, whichafter condensation yields a condensate consisting of equal parts ofbenzine and middle oil. When adding as catalyst chromic acid in the sameamount and under the same'reaction conditions, the same results can onlybe obtained by lowering the throughput to 85 per cent of that used withthe acid catalyst.

Example 7 Finely ground brown coal is soaked with such an amount ofsulphuric acid of 40 per cent strength, that per kilogram of dried coal'25 grams of sulphuric acid, calculated as 100 percent acid, are used.The coal is then made into a paste with an equal amount of heavy oil,obtained by destructive hydrogenation from the same coal, heatedtogether with hydrogen under a pressure of 200 atmospheres to 450 C. andpassed through a reaction vessel. 93 per cent of the. carbon of the coalis thereby obtained in the form of mainly liquid products. If the coalis not subjected to the acid-treatment, then the liquefaction is loweredby '7 per cent.

Instead of sulphuric acid, equivalent amounts of nitric acid, orbenzine-sulphonic acid together with molybdlc acid may also be used.

Example 8' into a reaction vessel. The reaction products are passedwithout releasing the pressure into a separator, from which 93 per centof vaporous products, of which 60 per cent boil below 325 C., arewithdrawn while 7 per cent ,of high boiling products containing thecatalyst are removed as a liquid. The vaporous products are subsequentlyconveyed together with hydrogen through a second reaction vesselmaintained at 425 C. and filled with tungsten sulphide. A product isthus formed of which 75 per cent consists of benzlne and middle oil. Thehigher boiling portion' of this product is separated by fractionalcondensation from the portion boiling up to 325 C. and is returned tothe second reaction vessel for further conversion into lower boilingproducts. Instead of the above mentioned coke also the light ashes anddust from a low temperature carbonization plant may be employed afterimpregnation with ammonium molybdate and subsequently with sulphuricacid.

Example 9 A mineral oil distillation residue from which constituentsboiling above 325 C. have been separated is heated up together withhydrogen un-.

der a pressure of 200 atmospheres to about 370 C. by means of hotgasesand vapors issuing from a reaction vessel. and passing in a heatregenerator in counter current to the said residue. The initial materialis then mixed with 1 per cent of its weight of a catalyst consisting ofan activated brown coal coke impregnated with 2 Der cent of itsweight'of molybdic acid, whereupon the whole is heated together withhydrogen in a preheater heated with gas to 470 C. and then introducedinto a reaction vessel. Before introducing the mixture into this vesselsulphonated paraflin wax is added thereto in an amount corresponding to0.1 per cent, with reference to the initial material, of combinedsulphur; in this manner a very active catalyst containing molybdenum andsulphur is obtained.

The reaction product is led from the reaction vessel into a separator,from which 93 per cent are carried off as a distillate consisting to theextent of per cent of constituents boiling above 325 C., while '7 percent of high boiling products containing the catalyst are removed as aliquid. The distillate is passed at 425 C. through a second reactionvessel which is filled with tungsten sulphide. A product is thus formedof which per cent consists of Ibezine and middle oil. The higher boilingportion which is separated from the products boiling below 325 C. byfractional condensation is returned into the second reaction vessel forfurther conversion into low boiling products.

Instead of the said brown coal coke also wood charcoal or similarmaterials may be used as carrier'material for the molybdic acid.

In the appended claims the expression simple acid salt of an inorganicacid is intended to cover only salts in which part of the hydrogen 01' anon-complex inorganic acid is replaced by a base.

What we claim is: 1. A process for the production of valuablehydrocarbons by treatment of distillable carbonaceous materialscontaining compounds having a basic reaction with an excess of treehydrogen at a temperature between 250 and 700 C. and under a pressure ofat least 50 atmospheres and in the presence of. a non-basic catalyst thestep of adding to the said initial materials before or during the saidtreatment an'acidic substance other than the catalyst selected from thegroup consisting of acids and acid salts in such an amount that at leastper cent of the said compounds are neutralized.

2. In the process as claimed in claim 1 the step of adding a simplesolid acid salt.

3. In the process as claimed in claim 1, the step of adding the acidicsubstance in an amount ranging between about 80 and per cent ofthe"amount required for neutralizing the compounds, having a basicreaction, which are present in the initial distillable carbonaceous, ma-

terials.

4. An improved process for catalytic destructive hydrogenation ofcarbonaceous materials containing basic substances which comprisesadding an acidic substance other than the cata'- lyst to the feed stockin quantity sumcient to substantially neutralize the basic constituentscontained therein and then subjecting the neutralized mixture to; theaction of free hydrogen at atemperature between about 250 and-700 0.,under pressure of at least 50 atmospheres and in the presence 01' anon-basic hydrogenation catalyst.

5. A continuous process according to claim 4 in which the feed materialcontaining the added acidic substance is passed through areaction zonecontaining the catalyst.

